CN104364229A - Synthesis of diamido gellants by using dane salts of amino acids - Google Patents
Synthesis of diamido gellants by using dane salts of amino acids Download PDFInfo
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- CN104364229A CN104364229A CN201380028791.2A CN201380028791A CN104364229A CN 104364229 A CN104364229 A CN 104364229A CN 201380028791 A CN201380028791 A CN 201380028791A CN 104364229 A CN104364229 A CN 104364229A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C231/00—Preparation of carboxylic acid amides
- C07C231/02—Preparation of carboxylic acid amides from carboxylic acids or from esters, anhydrides, or halides thereof by reaction with ammonia or amines
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C227/00—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton
- C07C227/14—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton from compounds containing already amino and carboxyl groups or derivatives thereof
- C07C227/18—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton from compounds containing already amino and carboxyl groups or derivatives thereof by reactions involving amino or carboxyl groups, e.g. hydrolysis of esters or amides, by formation of halides, salts or esters
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/0008—Detergent materials or soaps characterised by their shape or physical properties aqueous liquid non soap compositions
- C11D17/003—Colloidal solutions, e.g. gels; Thixotropic solutions or pastes
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/26—Organic compounds containing nitrogen
- C11D3/32—Amides; Substituted amides
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/22—Organic compounds
- C11D7/32—Organic compounds containing nitrogen
- C11D7/3263—Amides or imides
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/14—The ring being saturated
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Abstract
The invention relates to a method for the synthesis of a compound according to formula I comprising the following steps: a) reacting a Dane salt according to formula II and a Dane salt according to formula III with a coupling reagent; b) adding a diamine according to formula IV to the reaction mixture; and c) adding an acid to the reaction mixture to adjust the p H value of the reaction to <7; wherein L represents a C2-C20 alkyl group, a C6-C20 aryl group, or a C7-C20 alkylaryl group; R1 and R2 can be identical or different and represent a hydrogen atom, a C1-C4 alkyl group, a C1-C4 hydroxyalkyl group, a C1-C4 thioether group, a C6-C20 aryl group, a C7-C20 alkylaryl group, a C7-C20 alkylhydroxyaryl group, a C4-C20 alkylheteroaryl group with 1 to 4 heteroatoms; or a C1-C4 alkylcarboxylic moiety, which may be an acid, an amide, or which may be esterified with a C1-C6 alkyl group or a C7-C20 alkylaryl group; R3 represents a C1-C4 alkyl group; R4 represents a hydrogen atom, or a C1-C4 alkyl group; R5 represents a C1-C4 alkyl group; and X represents an alkali metal.
Description
The present invention relates to the method for being synthesized diamide base jelling agent by diamines and amino acid whose Deng's salt.
The diamide based compound of following general formula known in the art is used for thickening liquid composition as jelling agent:
Wherein, R
1and R
2be aminofunctional end group, and L is molecular weight is the linking group of 14-500g/mol.This type of jelling agent describes in such as WO 2011/112912A1 and WO 2011/112887A1.
Jelling agent is used to provide formation and comfortable quality to the liquid consumption product of such as liquid detergent composition.In addition, jelling agent can other component in stabilization product, such as enzyme and SYNTHETIC OPTICAL WHITNER.But, need conscientiously to select jelling agent, with the uncompatibility between other component preventing jelling agent and composition and unwanted side effect, the muddiness of such as liquid composition.
Diamide base jelling agent provides the significant advantage being better than other jelling agent, is that they and consuming product are widely compatible and does not affect the clarity of product.
The synthesis of diamide base jelling agent is described in WO 2011/112887A1.In that synthesis, use N, N '-dicyclohexylcarbodiimide makes N-benzyloxycarbonyl-Valine be coupled to diaminopropanes as coupling reagent.Therefore, the synthesis of known at present diamide base jelling agent needs the amino acid using N-benzyloxycarbonyl or N-(tert-butoxycarbonyl) to protect.But this type of synthetic method is expensive, mainly due to the amino acid whose cost of protection, and need extra step to remove protecting group.
Therefore, need for the synthesis of the more cheap of diamide base jelling agent and strategy faster.
For this reason, the invention provides the method for the compound of synthesis type I,
It comprises the following steps:
A) Deng's salt of formula II is made
With Deng's salt of formula III
React with coupling reagent;
B) in reaction mixture, add the diamines of formula IV
and
C) in reaction mixture, acid is added, so that the pH value of reactant is adjusted to <7;
Wherein
L represents C
2-C
20alkyl, C
6-C
20aryl or C
7-C
20alkylaryl;
R
1and R
2can be identical or different, and represent hydrogen atom, C
1-C
4alkyl, C
1-C
4hydroxyalkyl, C
1-C
4thioether group, C
6-C
20aryl, C
7-C
20alkylaryl, C
7-C
20alkyl hydroxy aryl, there is 1-4 heteroatomic C
4-C
20miscellaneous alkyl aryl;
Or C
1-C
4alkyl carboxylic acid groups, it can be acid, acid amides, or it can by C
1-C
6alkyl or C
7-C
20alkylaryl esterification;
R
3represent C
1-C
4alkyl;
R
4represent hydrogen atom or C
1-C
4alkyl;
R
5represent C
1-C
4alkyl; And
X represents basic metal.
Alkyl is linear, branching or cyclic hydrocarbon chain.It also can be linear, branching with the combination of ring texture.C
n-C
malkyl is the hydrocarbon with n-m carbon atom.
Aryl is aromatic hydrocarbon.Described aryl can be monocycle or many rings.When polyaromatic, each aromatic ring can be maybe can being connected by carbon-to-carbon singly-bound of condensing.The example of suitable aryl is phenyl, xenyl, naphthyl, anthryl or phenanthryl.C
n-C
maryl is the aromatic hydrocarbon with n-m carbon atom.
Heteroaryl is containing 1-4 heteroatoms, preferred 1-2 heteroatomic aromatic hydrocarbon.Described heteroatoms can be oxygen, sulphur and/or nitrogen.Described heteroaryl can be monocycle or many rings.Described heteroaryl can be connected to host molecule by its either carbon atom or nitrogen-atoms.
The aryl that alkylaryl is replaced by one or more alkyl.Described alkylaryl can be connected to host molecule by the carbon atom of its arbitrary alkyl or aryl.C
n-C
malkylaryl contains n-m carbon atom.
The heteroaryl that miscellaneous alkyl aryl is replaced by one or more alkyl.Described alkyl substituent can be connected to described heteroaryl by arbitrary aromatic carbon atom or nitrogen-atoms.Described miscellaneous alkyl aryl can be connected to host molecule by the carbon atom of the carbon atom of arbitrary alkyl and/or heteroaryl or nitrogen-atoms.
Hydroxyalkyl is the alkyl being optionally substituted with one or more hydroxyl replacement.C
1-C
4hydroxyalkyl contains 1-4 carbon atom.
Thioether group refers to two alkyl connected by thioether bond.C
1-C
4thioether group is altogether containing 1-4 carbon atom.Described thioether group can be connected to host molecule by its either carbon atom.
Alkyl hydroxy aryl is the wherein alkylaryl that is optionally substituted by a hydroxyl group of arbitrary aryl carbon atoms.Described alkyl hydroxy aryl can be connected to host molecule by the carbon atom of its arbitrary alkyl or aryl.C
n-C
malkyl hydroxy aryl contains n-m carbon atom.
C
1-C
4alkyl carboxylic acid groups can be acid, acid amides, or can by C
1-C
6alkyl or C
7-C
20alkylaryl esterification.When acid amides, the nitrogen of amide functional group is replaced by two hydrogen atoms.Alkyl group is linear, branching or cyclic hydrocarbon chain.It also can be linear, branching with the combination of ring texture.The aryl that described alkylaryl is replaced by one or more alkyl.Described alkylaryl can be connected to carboxylic acid fragment by the carbon atom of its arbitrary alkyl or aryl.C
1-C
4alkyl carboxyl is altogether containing 1-4 carbon atom.
By using the amino acid of Deng's salt form of formula II and III, present invention, avoiding the amino acid whose demand that N-benzyloxycarbonyl or N-(tert-butoxycarbonyl) are protected.In addition, the enamine group in formula II and III easily ruptures in acid condition and makes alpha-amino group deprotection.Therefore, protecting group is removed without the need to extra step.
Deng's salt of formula II and III is easily obtained by corresponding beta-keto carboxylicesters and amino acid whose base catalyzed reactions.As another advantage of the present invention, can be carried out in position by beta-keto carboxylicesters and Amino acid synthesis Deng salt, because do not need to be separated Deng's salt from this reaction mixture before step a).
Except as otherwise noted, for two of the connection Deng salt mentioned in the context of the present invention with R
3and R
4the mark of any E/Z isomer of double bond of carbon atom should be interpreted as other E/Z isomer all of this key also comprised for this compound.In the solution, usually there is the balance of E-configuration Deng's salt and Z-configuration Deng salt.
Preferably, R
1and R
2represent hydrogen atom, normal-butyl, the tertiary butyl, propyl group, cyclopropyl, ethyl independently, or the one in following amino acid whose side chain: the ester of L-Ala, α-amino-isovaleric acid, leucine, Isoleucine, methionine(Met), phenylalanine, tyrosine, tryptophane, Serine, Threonine, glutamine, l-asparagine, L-glutamic acid or the ester of aspartic acid.At this, statement " side chain " refers to the substituting group of the alpha-carbon atom being connected to a-amino acid.The ester of L-glutamic acid or aspartic acid is by C on pendant carboxylic acid group
1-C
6alkyl or C
7-C
20alkylaryl esterification.Preferably, the ester of L-glutamic acid or aspartic acid is esterified on pendant carboxylic acid group.For above-mentioned amino acid, described side chain is methyl, sec.-propyl, isobutyl-, sec-butyl, 2-methylsulfanyl-ethyl, benzyl, 4-hydroxybenzyl, 3-skatole base, methylol, 1-hydroxyethyl, formamido-ethyl, formamido-methyl, alkoxy carbonyl ethyl, alkoxycarbonylmethyl, aryl-alkoxy carbonyl ethyl or aryl-alkoxy carbonyl methyl.In a particularly preferred embodiment, R
1and R
2represent unsubstituted C independently
1-C
4alkyl.In another particularly preferred embodiment, R
1and R
2represent the one in following amino acid whose side chain independently: L-Ala, α-amino-isovaleric acid, leucine, Isoleucine or phenylalanine.
R
1and R
2can be identical or different.If R
1and R
2identical, then formula II is identical with Deng's salt of III, namely uses single Deng's salt to carry out the diamide based compound of synthesis type I.The diamide based compound obtained is substituted symmetrically.On the other hand, if R
1and R
2difference, then the diamide based compound of obtained formula I is the mixture of the diamide based compound differently replaced.
R
3preferred expression methyl.R
4preferred expression hydrogen.R
5preferred expression methyl or ethyl.In a particularly preferred embodiment, R
3represent methyl, R
4represent hydrogen, and R
5represent ethyl.In this case, Deng's salt of formula II and III can be synthesized by ethyl 3-oxobutanoate and corresponding amino acid whose reaction.
X preferably represents sodium atom or potassium atom.X more preferably represents potassium atom.
In particularly preferred embodiment of the present invention, Deng's salt of formula II and III is selected from following list.
Method of the present invention step a) in, Deng's salt of formula II and III and coupling reagent are reacted, obtain Deng's salt of activated amino acid.Deng's salt pair amino of described activated amino acid has reactivity, and the diamino compounds of itself and formula IV can be made to react, to make amino acid couplings to diamino compounds by forming amido linkage.Preferably, amino acid activates by forming mixed acid anhydride.The coupling reagent be applicable to for this object is such as pivalyl chloride, methylsulfonyl chloride, diphenyl phosphoryl chloride or isobutyl chlorocarbonate.Described coupling reagent also can represent one group of coupling reagent.
Reaction between Deng's salt of formula II and III and coupling reagent is carried out in the solution.Temperature of reaction is regulated according to the fusing point of solvent and the thermostability of boiling point and reagent.Described reaction preferably-10 DEG C to+30 DEG C, more preferably carry out at the temperature of 0 DEG C to 20 DEG C.
Preferably, the reaction between Deng's salt of formula II and III and coupling reagent is carried out in polar aprotic solvent.The solvent be applicable to for the present invention is such as methylene dichloride, methyl tertiary butyl ether, tetrahydrofuran (THF), ethyl acetate, isopropyl acetate, dimethyl formamide, acetonitrile, methyl-sulphoxide, methyl iso-butyl ketone (MIBK), methyl ethyl ketone, acetone or its mixture.
Preferably, first by Deng's salt suspension of formula II and III in a solvent.Or Deng's salt of formula II and III also can synthesize as mentioned above in position.Then, add coupling reagent, and stirred reaction mixture, until Deng's salt and coupling reagent complete reaction.Preferably, the reaction times is 12 hours at the most, more preferably 30 minutes to 2 hours.
The diamino compounds of preferred formula IV is that wherein L represents C
6-C
12those of linear alkyl, Isosorbide-5-Nitrae-Dimethylcyclohexyl or xylyl.In a particularly preferred embodiment, the diamino compounds of described formula IV is selected from following list.
H
2N-(CH
2)
12-NH
2
Step b) in reaction can with step a) in carry out at identical temperature.But, preferably, being joined by diamino compounds after in step reaction mixture a), temperature is adjusted to 10 DEG C to 30 DEG C.After adding diamino compounds, stirred reaction mixture, until reaction has reached.Preferably, reaction mixture is stirred to many 12 hours, more preferably 10 minutes to 1 hour.
Preferably, by diamino compounds and alkali, more preferably add together with non-nucleophilic alkali.The compound be applicable to for this object is such as triethylamine, diisopropylethylamine or its mixture.
In step b) after, by adding acid and water acidified reaction mixture.Acidifying causes the release of the hydrolysis of enamine group and the diamide based products of formula I.Preferably, by the pH regulator of reaction mixture to the value guaranteeing enamine group complete hydrolysis, be more preferably adjusted to the pH of 1-2.Preferably, described acid is salt aqueous acid.
The diamide based products of formula I can be carried out further in position processing or can in step c) after be separated from reaction mixture.Preferably, by the diamide based products of formula I in step c) after be separated from reaction mixture.This can realize in the following manner: with aqueous phase acid with the immiscible organic solvent extraction of water, be adjusted to alkaline pH subsequently, preferably higher than 10 pH, and with water immiscible organic solvent extraction diamide based products.Described diamide based products can by being further purified from organic phase crystallization.
In a preferred embodiment of the invention, method of the present invention step a) and b) in use polar aprotic solvent, step a) period at the temperature of 0 DEG C to 20 DEG C, in step b) period is at the temperature of 10 DEG C to 30 DEG C and in step c) in carry out under the pH of 1-2.In this embodiment, step a) in Deng's salt and coupler form mixed acid anhydride, and in step b) in, the reaction between step product a) and the diamino compounds of formula IV is carried out under the existence of non-nucleophilic alkali.
Embodiment
Embodiment 1
The synthesis of N-(3-oxyethyl group-1-methyl-3-oxo third-1-thiazolinyl)-Valine sylvite
Valine (117.2g, 1.0mol), KOH (85%, 66.0g, 1mol) and ethyl 3-oxobutanoate (140.2mL, 1.1mol) are dissolved in isopropyl acetate (1L).Dean-Stark apparatus (Dean-Stark apparatus) is used by reaction mixture to be heated to backflow.32mL water is isolated in 1.75h.Form a small amount of precipitation.Distill out 500mL.
Deng's salts solution is directly used in next step.
Analysis to the sample be separated:
1h-NMR (600MHz, CDCl
3, major rotomer): δ=9.12 (d, J=6Hz, 1H), 4.32 (s, 1H), 4.07-4.02 (m, 1H), 3.99-3.94 (m, 1H), 3.65-3.63 (m, 1H), 1.98-1.92 (m, 1H), 1.83 (s, 3H), 1.19 (t, J=12Hz, 3H), 0.88 (d, J=6Hz, 3H), 0.84 (d, J=6Hz, 3H) ppm.
Embodiment 2
The synthesis of N-(3-oxyethyl group-1-methyl-3-oxo third-1-thiazolinyl)-L-Phe sylvite
Deng's salt of L-Phe is prepared as described in example 1 above.
Analysis to the sample be separated:
1h-NMR (600MHz, D
2o, major rotomer): δ=7.34-7.30 (m, 2H), 7.27-7.24 (m, 3H), 4.36 (s, 1H) 4.21-4.19 (m, 1H), 4.03-3.98 (m, 2H), 3.15 (dd, J=12Hz, 6Hz, 1H), 2.93 (dd, J=12Hz, 6Hz, 1H), 1.69 (s, 3H), 1.16 (t, J=12Hz, 3H) ppm.
Embodiment 3
synthesis
Isopropyl acetate (1.77L) is joined in Deng's salts solution of embodiment 1, and mixture is cooled to 10 DEG C.Add pivalyl chloride (123.1mL, 1mol).Temperature is elevated to 17 DEG C.Reaction mixture is stirred 45min at 17 DEG C, and is cooled to 10 DEG C again.In independent flask, 1,12-diamino dodecane (91.1g, 0.46mol) is dissolved at 50 DEG C in isopropyl acetate (1.57L) and triethylamine (0.16L, 1.14mol).Solution is cooled to 10 DEG C.Join disposable for 1,12-diamino dodecane solution in Deng's salts solution.Temperature is elevated to 20 DEG C.Reaction mixture is at room temperature stirred 30min.Water (1.36L) is added in reaction mixture, and by adding dense HCl (0.51L) by pH regulator to 1-2.Distill out isopropyl acetate (about 3L).Isolate aqueous phase, and wash with isopropyl acetate (0.68L).Abandon organic phase.By aqueous phase concentrated (distilling out about 1L), and process with isopropyl acetate (1.0L).By adding NaOH solution (0.4L) by pH regulator to 10-11.Be separated at 70 DEG C.Be separated organic phase, and it is washed with water at 70 DEG C.Solution is cooled to 0 DEG C, and precipitation is leached, with the washing of cold isopropyl acetate (2 × 0.2L), and dry in vacuum at 60 DEG C.Yield: 121.4g (through 2 steps, 67%).
1H-NMR(600MHz,DMSO)：δ＝7.75(t,J＝6Hz,2H),3.10-2.99(m,4H),2.88(d,J＝6Hz,2H),1.85-1.80(m,2H),1.58(brs,4H),1.38(t,J＝6Hz,4H),1.23(s,16H),0.85(d,J＝6Hz,6H),0.78(d,J＝6Hz,6H)ppm。
Embodiment 4
synthesis
Use step in the same manner as in Example 3, except Deng's salts solution of embodiment 2 is used as intitation reagents.
1H-NMR(600MHz,DMSO)：δ＝8.51(t,J＝6Hz,2H),8.40(brs,4H),7.32-7.24(m,10H),4.00-3.97(m,2H),3.12-3.01(m,6H),2.93-2.87(m,2H),1.36-1.17(m,20H)ppm。
Embodiment 5
synthesis
Use step in the same manner as in Example 3, except Isosorbide-5-Nitrae-cyclohexyldimethylamine is used as diamines.
1H-NMR(600MHz,DMSO)：δ＝7.65(t,J＝6Hz,2H),3.21-3.11(m,4H),2.77(d,J＝6Hz,2H),2.10-2.04(m,2H)1.95-1.90(m,2H),1.62(brs,4H),1.51-1.42(m,4H),1.23-1.16(m,4H)0.89(d,J＝6Hz,6H),0.79(d,J＝6Hz,6H)ppm。
Claims (13)
1. the method for the compound of synthesis type I,
It comprises the following steps:
A) Deng's salt of formula II is made
With Deng's salt of formula III
React with coupling reagent;
B) in reaction mixture, add the diamines of formula IV
and
C) in reaction mixture, acid is added, so that the pH value of reactant is adjusted to <7;
Wherein
L represents C
2-C
20alkyl, C
6-C
20aryl or C
7-C
20alkylaryl;
R
1and R
2can be identical or different, and represent hydrogen atom, C
1-C
4alkyl, C
1-C
4hydroxyalkyl, C
1-C
4thioether group, C
6-C
20aryl, C
7-C
20alkylaryl, C
7-C
20alkyl hydroxy aryl, there is 1-4 heteroatomic C
4-C
20miscellaneous alkyl aryl;
Or C
1-C
4alkyl carboxylic acid groups, it can be acid, acid amides, or it can by C
1-C
6alkyl or C
7-C
20alkylaryl esterification;
R
3represent C
1-C
4alkyl;
R
4represent hydrogen atom or C
1-C
4alkyl;
R
5represent C
1-C
4alkyl; And
X represents basic metal.
2. the process of claim 1 wherein R
1and R
2can be identical or different, and represent hydrogen atom, normal-butyl, the tertiary butyl, propyl group, cyclopropyl, ethyl, or the one in following amino acid whose side chain: the ester of L-Ala, α-amino-isovaleric acid, leucine, Isoleucine, methionine(Met), phenylalanine, tyrosine, tryptophane, Serine, Threonine, glutamine, l-asparagine, L-glutamic acid or the ester of aspartic acid.
3. the method any one of claim 1-2, wherein L represents C
6-C
12linear alkyl, Isosorbide-5-Nitrae-Dimethylcyclohexyl or xylyl.
4. the method any one of claim 1-3, wherein R
3represent methyl.
5. the method any one of claim 1-4, wherein R
4represent hydrogen atom.
6. the method any one of claim 1-5, wherein R
5represent methyl or ethyl.
7. the method any one of claim 1-6, wherein X is Na or K.
8. the method any one of claim 1-7, the R in its Chinese style II and III
3and R
4phase cis-configuration each other.
9. the method any one of claim 1-8, wherein said coupling reagent is selected from pivalyl chloride, methylsulfonyl chloride, diphenyl phosphoryl chloride or isobutyl chlorocarbonate or its mixture.
10. the method any one of claim 1-9, wherein in step c) in, described pH value is adjusted to pH 1-2.
Method any one of 11. claim 1-10, wherein step a) in reaction carry out at the temperature of-10 DEG C to+30 DEG C.
Method any one of 12. claim 1-11, wherein step a) and b) in reaction carry out in polar aprotic solvent.
The method of 13. claims 12, wherein said solvent is selected from methylene dichloride, methyl tertiary butyl ether, tetrahydrofuran (THF), ethyl acetate, isopropyl acetate, dimethyl formamide, acetonitrile, methyl-sulphoxide, methyl iso-butyl ketone (MIBK), methyl ethyl ketone, acetone or its mixture.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US201261654741P | 2012-06-01 | 2012-06-01 | |
| US61/654,741 | 2012-06-01 | ||
| PCT/EP2013/059757 WO2013178450A1 (en) | 2012-06-01 | 2013-05-13 | Synthesis of diamido gellants by using dane salts of amino acids |
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| Publication Number | Publication Date |
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| CN104364229A true CN104364229A (en) | 2015-02-18 |
| CN104364229B CN104364229B (en) | 2016-07-06 |
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| CN201380028791.2A Expired - Fee Related CN104364229B (en) | 2012-06-01 | 2013-05-13 | By using amino acid whose Deng's salt synthesis diamides base gellant |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US9126896B2 (en) |
| EP (1) | EP2855422B1 (en) |
| JP (1) | JP2015518014A (en) |
| CN (1) | CN104364229B (en) |
| PT (1) | PT2855422T (en) |
| WO (1) | WO2013178450A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108273280A (en) * | 2018-02-08 | 2018-07-13 | 凯莱英医药集团（天津）股份有限公司 | The separator and method of acetonitrile-methyl tertiary butyl ether(MTBE)-aqueous systems |
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| CN101665443A (en) * | 2008-09-03 | 2010-03-10 | 上海五洲药业股份有限公司 | Method for preparing amino acid dane salt |
| WO2011112887A1 (en) * | 2010-03-12 | 2011-09-15 | The Procter & Gamble Company | Di-amido gellant for use in consumer product compositions |
| WO2011112910A1 (en) * | 2010-03-12 | 2011-09-15 | The Procter & Gamble Company | Liquid detergent compositions comprising ph tuneable amido-gellants, and processes for making |
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- 2013-05-13 JP JP2015514404A patent/JP2015518014A/en active Pending
- 2013-05-13 WO PCT/EP2013/059757 patent/WO2013178450A1/en active Application Filing
- 2013-05-13 CN CN201380028791.2A patent/CN104364229B/en not_active Expired - Fee Related
- 2013-05-13 US US14/386,540 patent/US9126896B2/en not_active Expired - Fee Related
- 2013-05-13 PT PT137230793T patent/PT2855422T/en unknown
- 2013-05-13 EP EP13723079.3A patent/EP2855422B1/en not_active Not-in-force
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108273280A (en) * | 2018-02-08 | 2018-07-13 | 凯莱英医药集团（天津）股份有限公司 | The separator and method of acetonitrile-methyl tertiary butyl ether(MTBE)-aqueous systems |
| CN108273280B (en) * | 2018-02-08 | 2023-10-27 | 凯莱英医药集团（天津）股份有限公司 | Separation device and method for acetonitrile-methyl tertiary butyl ether-water system |
Also Published As
| Publication number | Publication date |
|---|---|
| US9126896B2 (en) | 2015-09-08 |
| CN104364229B (en) | 2016-07-06 |
| EP2855422B1 (en) | 2016-07-13 |
| WO2013178450A1 (en) | 2013-12-05 |
| US20150073172A1 (en) | 2015-03-12 |
| JP2015518014A (en) | 2015-06-25 |
| EP2855422A1 (en) | 2015-04-08 |
| PT2855422T (en) | 2016-08-26 |
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